CN103435006A - High-CO high-conversion-rate isothermal shift reactor - Google Patents

High-CO high-conversion-rate isothermal shift reactor Download PDF

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CN103435006A
CN103435006A CN2013103640452A CN201310364045A CN103435006A CN 103435006 A CN103435006 A CN 103435006A CN 2013103640452 A CN2013103640452 A CN 2013103640452A CN 201310364045 A CN201310364045 A CN 201310364045A CN 103435006 A CN103435006 A CN 103435006A
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water
gas
converter
catalyst bed
steam
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CN103435006B (en
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谢定中
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Hu'nan Anchun High & New Technology Co Ltd
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Hu'nan Anchun High & New Technology Co Ltd
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Priority to PCT/CN2013/084160 priority patent/WO2015024287A1/en
Priority to US14/912,869 priority patent/US9993790B2/en
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Abstract

The invention discloses a high-CO high-conversion-rate isothermal shift reactor and a process using the high-CO high-conversion-rate isothermal shift reactor. The isothermal shift reactor comprises a shell, an inner cavity, an upper tube sheet and a lower tube sheet welded with water tubes, and a bottom tee joint; shell covers are respectively arranged at the upper end and the lower end of the shell, a water chamber and a steam chamber are arranged at the upper part of the inner cavity, an upper catalyst bed is arranged in the middle of the inner cavity, a lower catalyst bed is arranged at the lower part of the inner cavity, the water tubes are distributed on the upper catalyst bed, no water tube is arranged on the lower catalyst bed, a center tube is arranged in the inner cavity, the upper part of the center tube is located in the upper catalyst bed, the lower part of the center tube is located in the lower catalyst bed, the bottom tee joint is provided with an unreacted gas inlet, an exchange gas outlet and a steam and water mixture inlet, a steam and water mixture spray tube is sleeved in the center tube, and the reactor is equipped with different technological processes for the unreacted gas with different CO% and the converted gas with different CO%. The high-CO high-conversion-rate isothermal shift reactor can achieve low temperature, high CO, high conversion rate and small system resistance.

Description

The high interconversion rate isothermal of a kind of high CO shift-converter
Technical field
The present invention relates to that synthetic ammonia, methyl alcohol are synthetic, preparing ethylene glycol, coal liquefaction, coal preparing natural gas, hydrogen manufacturing and industrial furnace exhaust gas utilize field, relate in particular to the high interconversion rate reactor of a kind of high CO and technical process, relate in industrial furnace tail gas, industrial gas CO(the highest more than 85%) become hydrogen with steam reaction, realize shift-converter and the technique of high interconversion rate (being up to more than 98.5%).
Background technology
Coal gas, conversion of natural gas gas, coke(oven)gas reforming gas, calcium carbide stove exhaust, blast furnace gas etc., these gases all contain a large amount of CO, for example to contain CO be 80 % to calcium carbide tail gas, in coal gas CO content be 30%～68%(with coal gasification method different have different), the variable H be changed to of great use of CO 2, the reaction formula of its conversion is:
CO+H 2o(vapour)=CO 2+ H 2+ Q
Transformationreation is the heat release reversible reaction, and catalyzer and excessive H must be arranged 2o(water vapour) press reaction formula excessive, just can make reaction to generating H 2direction is carried out.
Catalyzer is cobalt, molybdenum transformation catalyst, and its activeconstituents is MoS.The use temperature scope of transformation catalyst is 230 ℃～470 ℃.
MoS 2+2H 2O＝MoO 2+2H 2S
From reaction formula, the CO conversion is thermopositive reaction, and liberated heat can make reactant gases heat up, and catalyzer synchronously reacts at this temperature.Every reaction 1%CO(wet basis), 9 ℃～10 ℃ of temperature rises (butt raises 5 ℃～6 ℃); In coal gas, CO content is higher, and after reaction, conversion gas CO content is lower, converts CO more, and temperature rise is higher.
For example: CO 65%(butt in coal gas), water-gas ratio R=1.15, CO8.6%(butt after conversion), press:
CO + H 2O = CO 2 + H 2 + Q
65 115 4.3 23.7
Calculating reacts away carbon monoxide △ CO; (65-△ CO)/(100+ △ CO)=0.086
△CO=52
Reaction heat: 9590cal/mol after reaction,
Emit heat: 52 * 9590=498680Kcal/h,
Cp： 9.01kcal/kmol℃，
Reacting rear material: 215kmol/h,
498680-=215×9.01×△t，
△t=257.43
If before reaction, temperature is 245 ℃, after the reaction, temperature is: 257.43+245=502.43 ℃;
This temperature is used top temperature higher than catalyzer, can have a strong impact on the activity of catalyzer.When unreacting gas CO is very high, enter reactor as 45% to 80%, one, a large amount of CO immediate responses, temperature rises suddenly, when particularly unreacting gas self is with a large amount of water vapor, has more promoted reaction, and so-called temperature runaway phenomenon occurs.How controlling the temperature of reaction process, make it to be no more than the maximum operation (service) temperature that catalyzer allows, is a dozen difficult problems; Another difficult problem of CO conversion is high interconversion rate, and conversion approaches terminal, more approaches balance, and impellent is less, and the conversion difficulty is larger.As the CO interconversion rate has reached 90%, (conversion gas CO is down to 1.5%) is down to 0.5% as different transform 1%(conversion gas CO again), needing increases by a terminal shift converter, and its catalytic amount is total amount 40%.Self is not with water vapor some unreacting gas, and as industrial furnace gas, semi-water gas etc., final interconversion rate is higher, adds excess steam more, and the steam consumption is larger.
The principle way addressed the above problem at present is: adopt the reaction of many stoves multistage insulation.As shown in Figure 1, gas preheating, to the catalyzer initial reaction temperature, is added a certain amount of steam, reaches certain gas to steam ratio, carry out transformationreation for the first time, CO converts a part, and in gas, CO is reduced to a certain degree, temperature rising (be no more than catalyzer and allow top temperature), reaction gas is cooling, temperature reduces (than catalyzer, allow minimum temperature slightly high, guarantee not condensation of steam, catalyst activity is higher); React for the second time, CO reduces again, temperature raise again (the same, as to be no more than catalyzer and to allow top temperature) more cooling (cooling temperature is as front principle); Carry out again transformationreation for the third time, reach the CO content of final needs.
As coal gas contains CO68.65%, water-gas ratio 1.45, 211 ℃ of temperature, through steam trap, E-1 isolates moisture, be heated to 296 ℃ through gas-gas heat exchanger E-2, parallel connection enters detoxification groove E-3, pre-stove E-4 and the detoxification groove E-5 of becoming, the pre-stove E-6 that becomes, CO is down to 35%, temperature rises to 380 ℃, through heat exchanger E-2, middle pressure vaporizer-condenser E-7 cooling, enter the 3rd shift converter E-8 reaction, CO is down to 6.7%, temperature rises to 434 ℃ through water spray cleaning device E-9, middle pressure vaporizer-condenser cooling E-10, through water of condensation well heater E-11, enter the 4th shift converter E-12 reaction, CO is down to 1%, temperature rise to 260 ℃, through low pressure vaporizer-condenser E-13, be cooled to 185 ℃ and enter again the 5th shift converter E-14 reaction, CO is down to 0.4%, temperature rises to 204 ℃, again through boiler water-suppling heater E-15, low pressure vaporizer-condenser E-16 steam separator E-17 leaves battery limit (BL).
There is following several problem in above-mentioned prior art:
1, containing CO68.65% coal gas, conversion gas is for ammonia processed or hydrogen manufacturing, be down to～0.4% interconversion rate requirement of its conversion gas CO is very high, needs four sections five shift converters more than 99%, needs shift-converter too many, a gas-gas heat exchanger is arranged, 6 cooler condensers, a spray cooling device therebetween; At least need 17 major equipments, equipment is too many thus, and connecting tube is too many; Floor space is large, and investment is many, and operation easier is large;
2, if do not convert, in gas, CO is up to 70%～86%, and equipment is more, and connecting tube is longer, uses four to five sections adiabatic conversion also can't realize conversion;
3, the CO of total amount 85% reacts away under 380 ℃～430 ℃, and high temperature makes catalysts easily aging, affects work-ing life, and the high-temperature reaction equipment pipeline is subject to thermal stresses large, and material requires high;
4, most of catalyst temperature reaches 400 ℃, and pyroreaction is unfavorable for chemical equilibrium, and reaching same interconversion rate needs catalyzer many;
5, reaction heat vapor condensation heat is for generation of low pressure (as 0.6MPa～2.5MPa) steam, and also has a large amount of water of condensation to discharge, and utilization ratio is low;
6, wherein E-9 adopts cold water directly to the reaction heat gas blowout, to drench the vaporization cooling, with the humid gas of water smoke, may make catalyst agglomeration or efflorescence, and impact is active, reduction of service life.
Summary of the invention
For existing high CO reactor above shortcomings, the present invention aims to provide the high interconversion rate isothermal of a kind of high CO shift-converter, and this reactor can be realized the high interconversion rate of CO, and systemic resistance is little.
To achieve these goals, the technical solution adopted in the present invention is:
The high interconversion rate isothermal of a kind of high CO shift-converter, comprise the shell with inner chamber, is positioned at upper tubesheet and the lower tubesheet on shell inner cavity top, is positioned at the threeway of shell inner cavity bottom; The two ends up and down of described shell all have end socket, and the cavity between the upper cover of this shell and described upper tubesheet is hydroecium, and the cavity between upper tubesheet and lower tubesheet is steam chest; Its constructional feature is, described hydroecium is communicated with the drum that is located at the shell top by water pipe, and this drum is communicated with described steam chest by pipeline; Described shell inner cavity middle part is provided with catalyst bed, this shell inner cavity bottom is provided with lower catalyst bed, there is annular space between described upper catalyst bed and inner walls, be provided with the supporting end socket between described upper catalyst bed and lower catalyst bed, described shell inner cavity is provided with pipe core, the top of this pipe core is positioned at catalyst bed, and the bottom of this pipe core is positioned at lower catalyst bed; The threeway of described bottom has unreacting gas entrance, conversion gas outlet and steam water interface entrance; Described upper catalyst bed is communicated with described unreacting gas entrance by annular space, and described lower catalyst bed is communicated with described conversion gas outlet; The steam water interface jet pipe is housed in described pipe core, and this steam water interface jet pipe is communicated with described steam water interface entrance.
Be below the technical scheme of further improvement of the present invention:
Further, for catalyst bed is carried out to temperature control, be provided with the many vertical vapour pipes of arranging in described upper catalyst bed.
Described vapour pipe has two kinds: two cover vapour pipes, U-shaped vapour pipe.A part of vapour pipe in described vapour pipe is two cover vapour pipes, and this pair of cover vapour pipe comprises inner tube and fill outer tube on inner pipe by support set; Elastic element is equipped with in the bottom of the described outer tube of closed bottom, and the bottom of described inner tube is communicated with described outer tube bottom, and the upper end of this inner tube is stretched out described outer tube and is communicated with described hydroecium, and the upper end of this outer tube is communicated with described steam chest.A part of vapour pipe in described vapour pipe is the U-shaped vapour pipe, and the right and left pipe of this U-shaped vapour pipe is not isometric, and the long side pipe of this U-shaped vapour pipe is communicated with described hydroecium, and the minor face pipe of this U-shaped vapour pipe is communicated with described steam chest.
Further, the vapour pipe be communicated with described hydroecium comprises inner tube and fills outer tube on inner pipe by supporting sleeve for two cover vapour pipes, this pair of cover vapour pipe; Elastic element is equipped with in the bottom of the described outer tube of closed bottom, and the bottom of described inner tube is communicated with described outer tube bottom.
For the ease of realizing the replacing of catalyzer, described upper catalyst bed top is provided with charging tube, and on this, the bottom of catalyst bed is provided with the loading and unloading material pipe; Described lower catalyst bed is communicated with described upper catalyst bed by being communicated with annular distance, and the bottom of this time catalyst bed is provided with lower discharge tube.
Further, the loadings of described upper catalyst bed accounts for the 48%-60% of total filling amount; The loadings of described lower catalyst bed accounts for the 40%-52% of total filling amount.
As a kind of concrete preferred embodiment, the profile of described support is B shape, and described elastic element is spring.
Effect in order to guarantee that the gas realization is sprayed, be equipped with horn-like breeder tube on the outer wall of described upper catalyst bed, the outer wall of lower catalytic bed and pipe core.
Further, second goal of the invention of the present invention has been to provide a kind of technique of utilizing the high interconversion rate isothermal of above-mentioned high CO shift-converter to carry out gas reforming, and this technique comprises the steps:
1), the coal gas of the CO that will be 40%～70% containing volumetric concentration successively through the first water separator, heat exchanger, purification except after malicious device, send into the not conversion gas entrance of the high interconversion rate isothermal of above-mentioned high CO shift-converter; Wherein, it is 230 ℃～240 ℃ that coal gas enters the temperature purified except malicious device, and the temperature that coal gas enters the isothermal shift-converter is 255 ℃～265 ℃;
2), conversion gas does not react in the isothermal shift-converter, the temperature in upper catalyst bed and lower catalyst bed is not 260 ℃～275 ℃, and after completion of the reaction, in conversion gas, the volumetric concentration of CO is 0.4%～0.7%;
3), conversion gas is sent battery limit (BL) from the conversion gas outlet enters heat exchanger, the first waste heat boiler, the second waste heat boiler, the second water separator, boiler water-suppling heater, water cooler, the 3rd water separator successively; Wherein to enter the temperature of heat exchanger be 255～265 ℃ to conversion gas, the temperature that conversion gas enters the second water separator is 170 ℃ ~ 190 ℃, the temperature that conversion gas enters water cooler is 75 ℃～80 ℃, and the temperature that conversion gas enters the 3rd water separator is 35 ℃～50 ℃.
Further, the boiler de-salted water of heating send drum, and the pressure saturation steam that the first waste heat boiler, the second waste heat boiler and drum produce is sent to respectively corresponding steam pipe system.
Thus, the boiler de-salted water of heating send drum, and as the make up water of shift converter Water, steam circulation and waste heat boiler, three kinds of pressure saturation steams of generation are sent to respectively corresponding steam pipe system.
Further, the 3rd goal of the invention of the present invention is to provide a kind of technique of utilizing the high interconversion rate isothermal of above-mentioned high CO shift-converter to carry out the industrial furnace gas conversion, and this technique comprises the steps:
The industrial furnace gas of the CO that will be 1), 45%～85% containing volumetric concentration enters oil eliminator through washing tower, the 4th water separator, strainer by the gas compressor compression successively, in the laggard heat exchanger of oil removing, after from heat exchanger, gas out enters successively and purifies except malicious device, advances the hydrocracking device, send in the high interconversion rate isothermal of above-mentioned high CO shift-converter; It is 200 ℃～225 ℃ that industrial furnace gas enters the temperature purified except malicious device, and the temperature that industrial furnace gas enters the isothermal shift-converter is 225 ℃～250 ℃;
2), industrial furnace gas reacts in the isothermal shift-converter, the temperature in upper catalyst bed and lower catalyst bed is 235 ℃～260 ℃, after completion of the reaction, conversion gas enters in steam-heated oven self-produced saturation steam drying from the conversion gas outlet;
3), from steam-heated oven conversion gas out successively by heat exchanger, boiler de-salted water well heater, deaerated water well heater, water cooler, the 5th water separator, sending battery limit (BL);
The conversion gas temperature that wherein enters heat exchanger is 230 ℃ ~ 255 ℃, and the conversion gas temperature that enters water cooler is 75 ℃～80 ℃, and the conversion gas temperature that enters the 3rd water separator is 35 ℃～50 ℃.
Further, the boiler de-salted water of heating is sent into drum, and self-produced saturation steam after drying, returns to the isothermal shift-converter and participates in transformationreation, in described shift-converter bottom, fills into the steam water interface in state of saturation.
Thus, the boiler de-salted water of heating send drum, as the make up water of shift converter Water, steam circulation, produces middle pressure steam and does the reaction vapor that this transformation system need add.Separately by the shift converter bottom, fill into the steam water interface in state of saturation, to improve reaction end chemistry quality of balance, improving final transformation efficiency.
Further, the 4th goal of the invention of the present invention is to provide a kind of technique of utilizing the high interconversion rate isothermal of above-mentioned high CO shift-converter to carry out the semi-water gas conversion, and this technique comprises the steps:
1), the semi-water gas of the CO that will be 25%～38% containing volumetric concentration through strainer, after enter in heat exchanger, from heat exchanger, gas out enters and purifies except malicious device, after send in the high interconversion rate isothermal of above-mentioned high CO shift-converter; Wherein, entering the semi-water gas temperature purified except malicious device is 210 ℃～230 ℃, and the semi-water gas temperature that enters the isothermal shift-converter is 230 ℃～250 ℃;
2), semi-water gas reacts in the isothermal shift-converter, the temperature in upper catalyst bed and lower catalyst bed is 235 ℃～260 ℃, after completion of the reaction, conversion gas enters in steam-heated oven self-produced saturation steam drying from the conversion gas outlet;
3), from steam-heated oven conversion gas out successively by heat exchanger, boiler water-suppling heater, de-salted water well heater, water cooler, the 6th water separator, sending battery limit (BL); The conversion gas temperature that wherein enters heat exchanger is 230 ℃ ~ 255 ℃, and the conversion gas temperature that enters water cooler is 75 ℃～80 ℃, and the conversion gas temperature that enters the 6th water separator is 35 ℃～50 ℃.
Further, the boiler de-salted water of heating is sent into drum, and self-produced saturation steam after drying, returns to the isothermal shift-converter and participates in transformationreation, in described shift-converter bottom, fills into the steam water interface in state of saturation.
Thus, the boiler de-salted water of heating send drum, as the make up water of shift converter Water, steam circulation, produces middle pressure steam and does the reaction vapor that this transformation system need add.Separately by the shift converter bottom, fill into the steam water interface in state of saturation, to improve reaction end chemistry quality of balance, improving final transformation efficiency.
Thus, the present invention is for industrial furnace tail gas, industrial gas CO(volumetric concentration 40%～85%), become hydrogen with steam reaction, and interconversion rate is up to more than 98%.90%～95% CO completes reaction in upper catalytic bed.Temperature of reaction is constant in the low temperature active scope, and different unreacting gas configuration different kinds of process flows to be transformed, formulate two kinds of typical process flow: the high water to steam ratio of high CO, mesohigh conversion; High CO hangs down water to steam ratio, low pressure conversion; And the high interconversion rate of low water to steam ratio.Advantage of the present invention operates with a shift converter and corresponding quick-reading flow sheets, simple being easy to, and realizes the high interconversion rate of CO content.Reaction heat by-product middle pressure steam, the solidifying high cooling water inflow of thermogenesis low-pressure steam thermo-efficiency of excess steam is few, catalyst life is long, and shift converter and systemic resistance are little.
Compared with prior art, the invention has the beneficial effects as follows:
1, the technology of the present invention core is that numerous water pipes are embedded in catalytic bed, and catalyzed reaction is emitted heat and absorbed and to be vaporizated into steam and to maintain bed temperature by water in water pipe.Its characteristics steam heat-transmission is very large, and all reaction heat can absorb immediately, guarantees that bed temperature is constant, stops the temperature runaway phenomenon, protects the catalyzer long period and efficiently moves; Temperature of reaction is low, and the balance temperature is apart from large, and the reaction impellent is large, and catalyst efficiency is high, and catalytic amount is few, and throughput is large;
2, in unreacting gas, CO can be up to more than 80%, and in conversion gas, CO can be down to the coal gas that 0.4%. makes pure oxygen water vapor and coal, and water to steam ratio 1.1～1.6 has been realized the complex transformations process of high CO, high interconversion rate, high water-gas ratio with a reactor.Reactor is few, and flow process is short;
3, due to above-mentioned advantage, only need to control drum pressure, just controlled the reaction whole process, temperature of reaction is constant, conversion gas CO is constant; Because above-mentioned reactor is few, flow process is short, make to convert the battery limit (BL) floor space little;
4, shift-converter is the low temperature isothermal reaction, and the low side (230 ℃～310) of its temperature in the catalyst activity scope, in 3 ℃～8 ℃ of the axial footpath of reaction bed maximum temperature differences.Make the catalyzer long service life.Make reactor without high temperature material;
5, all for generation of the 3.9MPa middle pressure steam, also can take full advantage of high water-gas ratio coal gas body brings a large amount of water vapors to reaction heat, participates in transformationreation, (existing technique is wanted steam in first condensation coal gas, after the first paragraph reaction, adds again steam and work of water sprinkling for better material moisture).Produce more remaining vapor condensation thermogenesis 1.2MPa and 0.6MPa steam, the cooling down water yield is few.In high water-gas ratio gas reforming flow process, low pressure steam can supply outward, in industrial furnace tail gas CO shift process, as the steam of reaction needed, the outer steam that supplies is greatly reduced.There is fine energy-saving effect;
6, temperature of reaction of the present invention is low, and steam-to-gas ratio is little, except constant temperature isothermal low-temperature shift converter, purification furnace, eventually become stove and all be made as radial structure, the reactor resistance only≤0.05MPa, systemic resistance≤0.2MPa;
7, aspect ratio is large, and single stove ability is large, easily maximizes; For example produce 1500 tons of synthetic ammonia daily, coal gas CO is 64%, and conversion gas CO is that 0.8%, one internal diameter, 4000 clear height 17M isothermal shift-converters get final product.
Below in conjunction with drawings and Examples, the present invention is further elaborated.
The accompanying drawing explanation
Fig. 1 is existing high CO gas reforming process flow sheet;
Fig. 2 is the structural representation of of the present invention pair of sleeve pipe;
Fig. 3 is the structure principle chart of an embodiment of the present invention;
Fig. 4 is the high CO conversion of the present invention shift process figure
Fig. 5 is the high CO shift process of industrial furnace tail gas of the present invention figure
Fig. 6 is semi-water gas shift process figure of the present invention.
Embodiment
Embodiment 1
In unreacting gas of the present invention, CO can be up to more than 85%, and in conversion gas, CO can be down to 0.4%.The shift-converter catalyzer is to take the cobalt of the anti-sulphur molybdenum type catalyzer that MOS, COS be Active components, the present invention is in the catalytic bed temperature, as long as higher than 30 ℃～40 ℃ of dew-point temperatures, to locate in active temperature low side scope (230 ℃～310 ℃), the reaction bed axle is maximum temperature difference only in 3 ℃～8 ℃ radially.
Isothermal shift-converter 5 integral body are round shape, as shown in Figure 3, and by upper tubesheet 2, charging tube 3, lower tubesheet 4, two cover vapour pipes 5, shell 6, on catalytic bed 7 radially, pipe core 8, U-shaped vapour pipe 9, annular communicating aperture 10, supporting end socket 11, steam water interface jet pipe 12, under catalytic bed 13 radially, loading and unloading material pipe 14, lower discharge tube 15, lock packing 16, bottom threeway and external drum 1 constitute.
On radially catalytic bed 7 numerous carbonated drink pipe 5,9 is arranged; Under radially catalytic bed 13 without water pipe.Two tube sheets 2,4 on catalytic bed are divided into steam chest and hydroecium by top, by upper Steam Pipe and down-take pipe, with drum 1, are communicated with respectively.
Upper and lower catalytic bed is all catalytic bed radially, is called overall diameter to reaction bed.Upper bed layer gas flows to center from neighboring, and lower bed layer gas is periphery stream outward from center.Radially on catalytic bed outer ring cylindrical shell and pipe core, tubaeform aperture is arranged, to guarantee gas, become the injection stream shape to advance bed, be uniformly distributed in the bed each point, radial flow arrangement greatly reduces the gas flow resistance.
The unreacting gas CO that has just entered catalytic bed radially is high, and water-gas ratio is high, and impellent is large, and speed of response is fast, and the CO that volumetric concentration is 60% is to be H2 and CO2 in upper radially catalytic bed 7 peripheral circles inner conversions, and the area of a circle of this annulus inner conduit is little, and pipe density is larger; The middle circle inner conduit, the area of a circle is large, and pipe density is less.
Described vapour pipe has two kinds: the periphery ring is two sleeve pipes 5, toward in, is U-shaped pipe 9, two sleeve pipe outer tube 18 lower end closed, and upper end is welded on lower tubesheet.Inner tube 17 is inserted in outer tube 18, and lower end is not sealed, and with outer tube 18 lower ends, keeps a segment distance, and upper end is welded on upper tubesheet.U-shaped pipe 9 is longer on one side, and its mouth of pipe is welded on upper tubesheet 2, and shorter one side mouth of pipe is welded on lower tubesheet 4.Two sleeve pipes density of arranging can be larger, but inner tube only plays guide functions, without heat transmission function, has increased on the contrary weight of equipment and cost; The relative merits of U-shaped pipe in contrast.
As shown in Figure 3,17,18 flexible " B " shapes of two sleeve pipe inner and outer pipes support 19, shimmy to prevent inner tube 17, are supported on inner tube 17 and stagger and arrange; There is taper little spring 20 outer tube 18 lower ends, make two sleeve pipes flexible flexible.
By the bottom threeway, entered containing CO coal gas, by along under annular space and go up, through upper radially catalytic bed 7 cylindrical shell apertures, radially through the catalytic bed reaction, CO is down to 3%～5%, enters pipe core 8, from top to bottom to hypomere diffluence pipe core, under radially catalytic bed 13 react.Radial flow is to periphery, and CO is down to 0.4%～1%, passes down radially catalytic bed cylindrical shell aperture, completes reaction.Go out reactor by bottom threeway 16.
The water intake chamber that drum 1 descends, through flowing into respectively U-shaped pipe 9 long side pipes and two sleeve pipe 5 inner tubes.Enter water in inner tube from top to bottom to bottom, be folded to outer tube, the outer reaction heat of absorption tube from bottom to top, water becomes steam water interface, rises to drum 1.Enter the water on U-shaped pipe 9 long limits, from top to bottom to bottom absorption tube, reaction heat makes the water section vaporization, and steam water interface is folded to U-shaped pipe 9 minor faces, from bottom to top, continues the outer reaction heat of absorption tube, and Geng Duoshui becomes steam water interface, rises to drum.Steam water interface separates in drum 1, and steam is sent outside, falls under water, completes a Water, steam circulation.
On radially catalytic bed 7 loadings account for total amount 48%～60%, under radially the catalytic bed loadings account for total amount 40%～52%,
Charging between upper lower tubesheet (catalyzer) pipe, its quantity is water pipe sum 8%～12%, and there is larger pipe centre, and the catalyzer that from then on charging tube adds passes by the annular communicating aperture 10 in the middle of end socket, and Ke Daxia is catalytic bed radially.
When catalyzer need be changed, spent catalyst in reactor should be drawn off.Loading and unloading material (catalyzer) pipe is to unload radially catalytic bed catalyzer, and symmetrical two are loaded on by around; Lower discharge tube is to unload radially catalytic bed catalyzer, symmetrical two.High pressure blind plate sealing for the discharge tube lower port, while preventing from normally moving, catalyzer falls.
Embodiment 2
As shown in Figure 4, the CO volumetric concentration matched with isothermal shift-converter of the present invention is 40%～70%, the gas reforming technical process of water-gas ratio 1.3～1.6, it is by the first water separator E-41, heat exchanger E-42, purify except malicious device E-43, E-44 isothermal shift-converter E-45, the first waste heat boiler E-46, the second waste heat boiler E-47, the second water separator E-48, boiler water-suppling heater E-49, water cooler E-410, the 3rd water separator E-411 forms.During work, contain the coal of CO through the first water separator E-41, enter heat exchanger E-42, unreacting gas is heated to 230 ℃～240 ℃, enter and purify except malicious device E-43, E-44, chlorine in gas, phosphorus, oxygen, hydrocarbon is eliminated herein, also there is a small amount of CO to be converted, after gas temperature rises to 255 ℃～265 ℃, enter isothermal shift-converter E-45, by the threeway of shift converter bottom, entered, carry out transformationreation at the stove internal catalyst bed, 260 ℃～275 ℃ of reaction bed temperatures, after reaction, conversion gas CO volumetric concentration is 0.7% left and right, from the bottom threeway, come out of the stove, the thermal change ventilation is through heat exchanger E-42, through the first waste heat boiler E-46, produce 1.2MPa steam, conversion gas is through the second waste heat boiler E-47, produce 0.6MPa steam, three kinds of self-produced saturation steams of pressure are sent relevant pressure level pipe network outside, the conversion gas temperature is down to 255～265 ℃, through the second water separator E-48, the conversion gas temperature drops to 180 ℃ of left and right, the excess steam condensation, its sensible heat, the waste heats such as heat of condensation produce respectively 1.3MPa and 0.6MPa steam, through boiler water-suppling heater E-49 successively by the boiler de-salted water, the heating of (going) deaerated water, after temperature is down to 75 ℃～80 ℃, be cooled to 40 ℃ through water cooler E-410 with circulating water again, the a large amount of condensations of conversion gas steam, through the one or three water separator E-411, by condensed moisture from, conversion gas is sent battery limit (BL).
The boiler de-salted water of heating send drum, as the make up water of shift converter Water, steam circulation, and the feedwater of low pressure steam generator, produce steam and send outside.
Embodiment 3
As shown in Figure 5, the CO50% matched with isothermal shift-converter of the present invention～85% industrial furnace gas (as acetylene furnace gas, steel-making converter, yellow phosphorus furnace gas) conversion process flow process.
The industrial furnace gas characteristics are C0% content high (40%～85%), basically are not with water vapor, sulfur-bearing not substantially, but dust content is many, and oxygen level is more, and the acetylene furnace gas is also containing unsaturated hydrocarbons.
As shown in Figure 5, with the isothermal conversion process match flow process by E-51 washing tower, E-52 water separator, strainer E-53, E-54, compressor E-55, oil eliminator E-516 in parallel, purify except malicious device E-56, E-57, hydrocracking device E-517, isothermal shift-converter E-58, steam-heated oven E-59, heat exchanger E-510, boiler de-salted water well heater E-511, deaerated water well heater E-512, air cooler E-513, the 5th water separator E-514, drum E-515 form.
Industrial furnace gas enters washing tower E-51, dust is washed with recirculated water, through the 4th water separator E-52 by gas band moisture from, again through the strainer E-53 of two parallel connections, E-54 (one is filtered another cleaning), dust is removed to extremely～0.1mg, be compressed to 1.8MPa～2.3MPa through gas compressor E-55 and enter heat exchanger E-510, unreacting gas is heated to 200 ℃～225 ℃, enter purification in parallel except malicious device E-56, E-57, chlorine in gas, phosphorus, oxygen, hydrocarbon is removed at this, also there is a small amount of CO to be converted, gas temperature rises to 2250 ℃～250 ℃, enter hydrocracking device E-517, after hydrocracking, enter isothermal shift-converter E-58 by the bottom threeway, carry out transformationreation at the stove internal catalyst bed, 235 ℃～260 ℃ of reaction bed temperatures, after reaction, conversion gas CO is down to 0.7% left and right, reach the conversion process requirement, from the bottom threeway, come out of the stove, the thermal change ventilation is through steam-heated oven E-59, by self-produced saturation steam drying, temperature is down to 230 ℃～255 ℃ left and right, conversion gas is gas after heat exchanger E-510 adds thermo compression, through boiler de-salted water well heater E-511, successively the boiler de-salted water is heated, through deaerated water well heater E-512 preheating (going) deaerated water, temperature is down to 75 ℃～80 ℃, through air cooler E-513, be cooled to 40 ℃ with air-cooled (or circulating water), the a large amount of condensations of conversion gas steam, through the 5th water separator E-514, by condensed moisture from, conversion gas is sent battery limit (BL).
The boiler de-salted water of heating send drum, as the make up water of shift converter Water, steam circulation, produces middle pressure steam and does the reaction vapor that this transformation system need add.Separately by the shift converter bottom, fill into the steam water interface in state of saturation, to improve reaction end chemistry quality of balance, improving final transformation efficiency.
Embodiment 4
As shown in Figure 6, the approximately CO30% matched with isothermal shift-converter of the present invention～CO38% semi-water gas conversion process flow process, though semi-water gas CO is not high, but during synthetic ammonia processed, require conversion gas CO very low, be 0.4%～0.6%, and coal gas dust content, oil-containing, containing oxygen, chloride, be not with water vapor, the present invention's flow process that matches is the strainer E-61 through two parallel connections, E-62 (one is filtered another cleaning), by dust tar dedusting oil removal filter, remove dust, greasy dirt, enter heat exchanger E-67, unreacting gas is heated to 210 ℃～230 ℃, enter purification in parallel except malicious device E-63, E-64, by oxygen in coal gas, chlorine, the nuisances such as phosphorus are removed, a small amount of CO conversion is also arranged, gas temperature rises to 230 ℃～250 ℃, enter isothermal shift-converter E-65 by the bottom threeway, carry out transformationreation at the stove internal catalyst bed, 230 ℃～265 ℃ of bed temperatures, after reaction, conversion gas CO is down to 0.4%～0.7 left and right, reach the conversion process requirement, from the bottom threeway, come out of the stove, the thermal change ventilation is through steam-heated oven E-66, by self-produced saturation steam drying, temperature is down to 230 ℃～255 ℃ left and right, through heat exchanger E-67 heating semi-water gas, through boiler water-suppling heater E-68, successively the boiler de-salted water is heated, through de-salted water well heater E-69 preheating (going) deaerated water, temperature is down to 75 ℃～80 ℃, be cooled to 40 ℃ through water cooler E-610 with circulating water, the a large amount of condensations of conversion gas steam, through the 6th water separator E-611, by condensed moisture from, conversion gas is sent battery limit (BL).
The boiler de-salted water of heating send drum, as the make up water of shift converter Water, steam circulation, produces middle pressure steam and does the reaction vapor that this transformation system need add.Separately by the shift converter bottom, fill into the steam water interface in state of saturation, to improve reaction end chemistry quality of balance, improving final transformation efficiency.
CO percentage ratio in the present invention all means volumetric concentration.
The content that above-described embodiment is illustrated should be understood to these embodiment only for being illustrated more clearly in the present invention, and be not used in, limit the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.

Claims (14)

1. the high interconversion rate isothermal of a high CO shift-converter, comprise the shell (6) with inner chamber, is positioned at upper tubesheet (2) and the lower tubesheet (4) on shell (6) inner chamber top, is positioned at the threeway (16) of shell (6) intracavity bottom; The two ends up and down of described shell (6) all have end socket, and the cavity between the upper cover of this shell (6) and described upper tubesheet (2) is hydroecium, and the cavity between upper tubesheet (2) and lower tubesheet (4) is steam chest; It is characterized in that, described hydroecium is communicated with the drum (1) that is located at shell (6) top by water pipe, and this drum (1) is communicated with described steam chest by pipeline; Described shell (6) inner chamber middle part is provided with catalyst bed (7), this shell (6) inner chamber bottom is provided with lower catalyst bed (13), there is annular space between described upper catalyst bed (7) and housing (6) inwall, be provided with supporting end socket (11) between described upper catalyst bed (7) and lower catalyst bed (13), described shell (6) inner chamber is provided with pipe core (8), the top of this pipe core (8) is positioned at catalyst bed (7), and the bottom of this pipe core (8) is positioned at lower catalyst bed (13); The threeway of described bottom has unreacting gas entrance, conversion gas outlet and steam water interface entrance; Described upper catalyst bed (7) is communicated with described unreacting gas entrance by annular space, and described lower catalyst bed (13) is communicated with described conversion gas outlet; Steam water interface jet pipe (12) is housed in described pipe core (8), and this steam water interface jet pipe (12) is communicated with described steam water interface entrance.
2. the high interconversion rate isothermal of high CO according to claim 1 shift-converter, is characterized in that, is provided with the many vertical vapour pipes (5,9) of arranging in described upper catalyst bed (7).
3. the high interconversion rate isothermal of high CO according to claim 2 shift-converter, it is characterized in that, a part of vapour pipe in described vapour pipe (5,9) is two cover vapour pipes, and this pair of cover vapour pipe comprises inner tube (17) and be sleeved on the outer tube (18) on inner tube (17) by supporting (19); Elastic element (20) is equipped with in the bottom of the described outer tube (18) of closed bottom, the bottom of described inner tube (17) is communicated with described outer tube (18) bottom, the upper end of this inner tube (17) is stretched out described outer tube (18) and is communicated with described hydroecium, and the upper end of this outer tube (18) is communicated with described steam chest.
4. according to the high interconversion rate isothermal of the described high CO of claim 2 or 3 shift-converter, it is characterized in that, described vapour pipe (5,9) a part of vapour pipe in is the U-shaped vapour pipe, the right and left pipe of this U-shaped vapour pipe is not isometric, the long side pipe of this U-shaped vapour pipe is communicated with described hydroecium, and the minor face pipe of this U-shaped vapour pipe is communicated with described steam chest.
5. the high interconversion rate isothermal of high CO according to claim 1 and 2 shift-converter, is characterized in that, described upper catalyst bed (7) top is provided with charging tube (3), and the bottom of catalyst bed on this (7) is provided with loading and unloading material pipe (14); Described lower catalyst bed (13) is communicated with described upper catalyst bed (7) by being communicated with annular distance, and the bottom of this time catalyst bed (13) is provided with lower discharge tube (15).
6. the high interconversion rate isothermal of high CO according to claim 1 and 2 shift-converter, is characterized in that, the loadings of described upper catalyst bed (7) accounts for the 48%-60% of total filling amount; The loadings of described lower catalyst bed (13) accounts for the 40%-52% of total filling amount.
7. the high interconversion rate isothermal of high CO according to claim 3 shift-converter, is characterized in that, the profile of described support (19) is B shape, and described elastic element (20) is spring.
8. the high interconversion rate isothermal of high CO according to claim 1 and 2 shift-converter, is characterized in that, on the outer wall of described upper catalyst bed (7), the outer wall of lower catalytic bed and pipe core (8), is equipped with horn-like breeder tube.
9. a technique of utilizing the high interconversion rate isothermal of the described high CO of one of claim 1-8 shift-converter to carry out gas reforming, is characterized in that, comprises the steps:
The coal gas of the CO that will be 1) 40%～75% containing volumetric concentration removes malicious device (E-43, E-44) afterwards through the first water separator (E-41), heat exchanger (E-42), purification successively, sends into the not conversion gas entrance of one of claim 1-8 described high CO high interconversion rate isothermal shift-converter (E-45); It is 230 ℃～240 ℃ that coal gas enters the temperature purified except malicious device (E-43, E-44), and the temperature that coal gas enters isothermal shift-converter (E-45) is 255 ℃～265 ℃;
2) conversion gas does not react in isothermal shift-converter (E-45), and the temperature in upper catalyst bed (7) and lower catalyst bed (13) is 260 ℃～275 ℃, and after completion of the reaction, in conversion gas, the volumetric concentration of CO is 0.4%～0.7%;
3), conversion gas is sent battery limit (BL) from the conversion gas outlet enters heat exchanger (E-42), the first waste heat boiler (E-46), the second waste heat boiler (E-47), the second water separator (E-48), boiler water-suppling heater (E-49), water cooler (E-410), the 3rd water separator (E-411) successively; Wherein to enter the temperature of heat exchanger (E-42) be 255～265 ℃ to conversion gas, the temperature that conversion gas enters the second water separator (E-48) is 170 ℃ ~ 190 ℃, the temperature that conversion gas enters water cooler (E-410) is 75 ℃～80 ℃, and the temperature that conversion gas enters the 3rd water separator (E-411) is 35 ℃～50 ℃.
10. technique of carrying out gas reforming according to claim 9, it is characterized in that, the boiler de-salted water of heating is sent into drum (1), and three kinds of pressure saturation steams that the first waste heat boiler (E-46), the second waste heat boiler (E-47) and drum (1) produce are sent to respectively corresponding steam pipe system.
11. a technique of utilizing the high interconversion rate isothermal of the described high CO of one of claim 1-8 shift-converter to carry out the industrial furnace gas conversion, is characterized in that, comprises the steps:
The industrial furnace gas of the CO that will be 1) 45%～85% containing volumetric concentration passes through successively washing tower (E-51), the 4th water separator (E-52), strainer (E-53, E-54) and enters oil eliminator (E-516) by gas compressor (E-55) compression, in the laggard heat exchanger of oil removing (E-510), from heat exchanger (E-510), gas out enters successively and purifies except malicious device (E-56, E-57), advance hydrocracking device (E-517) after, send in one of claim 1-8 described high CO high interconversion rate isothermal shift-converter (E-58); It is 200 ℃～225 ℃ that industrial furnace gas enters the temperature purified except malicious device (E-56, E-57), and the temperature that industrial furnace gas enters isothermal shift-converter (E-58) is 225 ℃～250 ℃;
2) industrial furnace gas reacts in isothermal shift-converter (E-58), temperature in upper catalyst bed (7) and lower catalyst bed (13) is 235 ℃～260 ℃, after completion of the reaction, conversion gas enters in steam-heated oven (E-59) self-produced saturation steam drying from the conversion gas outlet;
3) from steam-heated oven (E-59) conversion gas out successively by heat exchanger (E-510), boiler de-salted water well heater (E-511), deaerated water well heater (E-512), water cooler (E-513), the 5th water separator (E-514), sending battery limit (BL);
Wherein to enter the temperature of heat exchanger (E-510) be 230 ℃ ~ 255 ℃ to conversion gas, and the temperature that conversion gas enters water cooler (E-513) is 75 ℃～80 ℃, and the temperature that conversion gas enters the 3rd water separator (E-514) is 35 ℃～50 ℃.
12. technique of carrying out the industrial furnace gas conversion according to claim 11, it is characterized in that, the boiler de-salted water of heating is sent into drum (1), self-produced saturation steam after drying, return to isothermal shift-converter (E-58) and participate in transformationreation, in described shift-converter (E-58) bottom, fill into the steam water interface in state of saturation.
13. a technique of utilizing the high interconversion rate isothermal of the described high CO of one of claim 1-8 shift-converter to carry out the semi-water gas conversion, is characterized in that, comprises the steps:
The semi-water gas of the CO that will be 1) 25%～38% containing volumetric concentration enters in heat exchanger (E-67) after strainer (E-61, E-62), from heat exchanger (E-67), gas out enters to purify except after malicious device (E-63, E-64) and sends in one of claim 1-8 described high CO high interconversion rate isothermal shift-converter (E-65); Wherein, entering the semi-water gas temperature purified except malicious device (E-63, E-64) is 210 ℃～230 ℃, and the semi-water gas temperature that enters isothermal shift-converter (E-65) is 230 ℃～250 ℃;
2) semi-water gas reacts in isothermal shift-converter (E-65), temperature in upper catalyst bed (7) and lower catalyst bed (13) is 235 ℃～260 ℃, after completion of the reaction, conversion gas enters in steam-heated oven (E-66) self-produced saturation steam drying from the conversion gas outlet;
3) from steam-heated oven (E-66) conversion gas out successively by heat exchanger (E-67), boiler water-suppling heater (E-68), de-salted water well heater (E-69), water cooler (E-610), the 6th water separator (E-611), sending battery limit (BL); Wherein to enter the temperature of heat exchanger (E-67) be 230 ℃ ~ 255 ℃ to conversion gas, and the temperature that conversion gas enters water cooler (E-610) is 75 ℃～80 ℃, and the temperature that conversion gas enters the 6th water separator (E-611) is 35 ℃～50 ℃.
14. technique of carrying out the semi-water gas conversion according to claim 13, it is characterized in that, the boiler de-salted water of heating is sent into drum (1), self-produced saturation steam after drying, return to isothermal shift-converter (E-65) and participate in transformationreation, in described shift-converter (E-65) bottom, fill into the steam water interface in state of saturation.
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